Composition of matter and method of making same



Patented Sept. 12, 1944 I COMPOSITION OF MATTER AND METHOD OF MAKING SALIE Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd'.', Wilmington, Del., a corporation of Delaware No Drawing. Application August 2, 1943, Serial No. 497,126

9 Claims. ((1260-4043) c This invention relates to a new chemical prod- Glycerol may be conveniently indicated by the not or composition of matter, our present applifollowing formula: cation being a continuation-in-part of our copending application Serial No, 447,159, filed June 15, 1942,. 5 CaHla a The main object of our invention is to provide a new chemical product or compound that is particularly adapted for use as a demulsifier in the If treated with an oxyalkylating agent, and mo-,

resolution of crude oil emulsions. mentarily consideration Will be limited to an oxy- Another object of our invention is to provide 1 ethylating agent, one may obtain an oxyethylated a practicable method for manufacturing said new glycerol of the following formula:

chemical product or compound.

Although one of the primary objects of our (CZHKDNH invention is to provide a new compound or com- OaH50a(CzH40)fl'H position of matter that is an efficient demulsifier for crude oil emulsions of the water-in-oil type, the said compound or composition of matter is in which the value of n may vary from 3 to adapted for use in other arts, as hereinafter inand all the values of n need not be identical. dicated. It also may have additional uses in varif If a polybasic carboxy acid be indicated by the ous other fields which have not yet been investiformula: gated.

We have discovered that if one oxyalkylates COOH glycerol so as to introduce at least three oxyal- R000H kylene radicals for each hydroxyl group, and if OOOH the product so obtained is reacted with a polybasic carboxy acid having not over eight carbon then the acyclic reaction product of one mole of atoms, and in such a manner as to yield a fracoxyethylated glycerol and one mole of a polytional ester, due to the presence of at least one basic carboxy acid may be indicated by the folfree carboxyl radical, one can then esterify said 7 lowing formula:

acidic material or intermediate product with at least one mole of an alcoholic compound of the (CZHO)"'OOCR(COOH)"" type herein described to give a variety of new OaH5Os(CzH4O) compositions of matter which have utility in vari- (0,340); ous arts, and particularly in the demulsification of crude oil. 3 in which n" has the value of one or two. Simi- The compounds herein contemplated may be larly, if two moles of the polybasic acid be used, produced in any suitable manner, but are usually then the compound may be indicated by the folmanufactured by following one of two general lowing formula: v procedures. In one of said procedures the oxyalkylated glycerol, which is, in essence, a poly- 4O (C2HO)"'OOOR(OOOH)"" hydric alcohol, is reacted with a polybasic acid so CaHs a(C2H40) 'OOOR(COOH)n" as to give an acidic material or intermediate prod- (chmmflfl uct, which, in turn, is reacted with an alcoholic body of the kind hereinafter described, and mo- Likewise, if three moles of a polybasic acid are mentarily indicated by the formula R1(OH)m. employed, the compound may be indicated by Generically, the alcoholic body herein contemthe following formula: plated may be considered a member of the class in which m may vary from 1 to 10, although the specific significance of m in the present instance 3H 3-(C2H40)n'0OCR(OO0H)n" will be hereinafter indicated. The second pro- (OQHMMOOOMOOOED'LH cedure is to react an alcohol of the formula type R1 (OI-Um with a polybasic acid so as to produce If a fractional ester of the kind e mplified by an intermediate product, and then react said the three preceding formulae is reacted with one intermediate product or fractional ester with the r e es o an h I 0f he kind p selected oxyalkylated glycerol. ously described in a generic sense as R1(OH)m,

then obviously, one may obtain a material of the type indicated by the following formula:

[(OzHiO) OOCR(COOH) ""12 inwhichxisO, 1 or 2,yis 0, 1 or2, andzis 1, 2 or 3, and a." isOor 1,andy islor 2.

It has been previously stated that compounds of the type herein contemplated may be obtained by oxyalkylating agents, without being limited to ethylene oxide. Suitable oxyalkylating agents include ethylene oxide, propylene oxide, butylene oxide and glycid, which, although not included, strictly speaking, by the unitary structure is included within the meaning of the hereto in which replaces the numbers 2, 3 or 4, and Z includes the acidic hydrogen atom itself. In the above formula and hereafter, for convenience, R1 'is intended to include any hydroxyl groups that remain.

' If the compounds herein contemplated are obtained under usualconditio-ns, at the lowest temperatures, then the monomeric form is most likely to result. g

The production of the compounds herein contemplated is the result of one or more sterification steps. As is well known, esterification procedures can be carried out in various manners, but generally speaking, esterifications can be. carried out at the lowest feasibletemperatures by using one or several procedures. One procedure is to pass an inert dried gas through the mass to be esterified, and have present at the same time a small amount of a catalyst, such as dried I-ICl gas, a dried sulfonic acid, or the like; Another and better procedure, in many instances, is to employ the vapors of a suitable liquid, so as to remove any water formed and condense both the vapors of the liquid employed and the water in sucha manner as to trap out the water and return the liquid to the reacting yessel. This procedure is commonly employed in the arts, and for convenience, referenceis made to U. S. Patent No; 2,264,759, dated December 2,1941, to Paul C. Jones.

compounds are not absolutely isomers of the' monomeric compounds, but since, for all practical purposes, they can be so indicated, and since such practice is common in the arts concerned. with materials of this type, it is so adopted here. Thus, reference in the appended claims to polymers is intended to include the self-esterification products of the monomeric compounds.

V In view of what has been said, and in view of the recognized hydrophile properties of the recurring oxalkylene linkages, particularly the oxyethylene linkage, it is apparent that the materials herein contemplated may vary from compounds which are clearly water-soluble through selfemulsifying oils, to materials which are balsamlike and sub-resinous or semi-resinous in nature. The compounds may vary from monomers to polymers, in which the unitary structure appears a number of times, for instance, 10 or 12 times. It is to be noted that true resins, i. e., truly insoluble materials of a hard plastic nature, are not herein included. In other words, the polymerizedcompounds are soluble to a fairly definite extent; for instance, at least 5% in some solvents, such as water, alcohol, benzene, dichloroethyl ether, acetone,'cresylic acid, acetic acid, ethyl acetate, dioxane, or the like. This is simply another way of stating that the polymerized product contemplated must be of the sub-resinous type, which is commonly referred to as an A resin, or a B resin, as distinguished from a C resin, which is a highly lnfusible, insoluble resin (see Ellis, Chemistry of Synthetic Resins (1935), pages 862, et seq).

Reviewing the form as presented, it is obvious that one may obtain compounds within the scope disclosed, which contain neither a free hydroxyl nor a free carboxyl group, and one may also obtain a compound of the type in which there is present at least one free carboxyl, or at least one free hydroxyl, or both. The word "polar has sometimes been used in the arts in this particular sense to indicate the presence of at least one free hydroxyl group, or at least, one free carboxyl group, or both. In the case of the free carboxyl group, the carboxylic hydrogen atom may, of course, be replaced by any ionizable hydrogen atom equivalent, such, for example, as a metal, an ammonium radical, a substituted ammonium radical, etc. In the hereto appended claims the word polar is used in this specific sense.

' more than three hydroxyl groups, for instance,

they may be derived'from acyclic diglycerol, triglycerol, tetraglycerol, mixed polyglycerols, mannitol, sorbitol, various hexitols, dulcitol, pentae rythritol, sorbitan, mannitan, dipentaerythritol monoether, and other similar compounds. Such particular types in whichhigher hydroxylated materials are subjected to oxyalkylation and then employed in the same manner as oxyalkylated glycerol, is employed in the present instance, are

not contemplated in this specific case, although attention is directed to the same.

Reference is also made to other oxyalkylated compounds which may be used as reactants to replace oxyalkylated glycerol, or oxyalkylated ethylene glycol, which latter reactant is described in an application hereinafter referred to. The reactants thus contemplated include the type in which there is an amino or amido nitrogen atom. Particularly, when present in a low molal type of compound prior to oxyalkylation, reference being made to polyhydroxylated materials, including those having two or three hydroxyl groups, as

well as those having more than three hydroxyl groups. For instance, the oxyalkylated derivatives, particularly the oxyethylated derivatives of ethyldiethanolamine, bis(hydroxyethyl)acetamide, the acetamide of tris(hydroxymethyl) aminomethane, tetrahydroxylated ethylene diamine, etc. Compounds may also be derived from cyclic diglycerol and the like.

Furthermore, for convenience, attention is directed to a somewhat similar class of materials which are described in our application Serial No. 384,601, filed March 21, 1941, now U. S. Patent No. 2,295,169, dated September 8, 1942. Said patent involves the use of the same typ of alcoholic bodies for reactants, but is limited, among other things, to the compound which are essentially symmetrical in nature, for instance, involving the introduction of two alcoholic residues, whereas, in the present instance, one, two, or three, or more, might b introduced.

As indicated previously, the polybasic acids em ployed are limited to the type having not more than eight carbon atoms, for example, oxalic, malonic, succinic, glutaric, adipic, maleic and phthalic. Similarly, one may employ acids such as fumaric, glutaconic, and various others, such as citric, malic, tartaric, and the like. The selection of the particular tribasic or dibasic acid employed, is usually concerned largely with the con venience of manufacture of the finished ester, and also the price of the reactants. Generally speaking, phthalic acid or anhydride tends to produce resinous materials, and greater care must be employed if the ultimate or final product be of a ubresinous type. Specifically, the preferred type of polybasic acid is such as to contain six carbon atoms or less. Generally speaking, the higher the temperature employed, the easier it is to obtain large yields of esterified product, although polymerization may be stimulated. be comparatively cheap, but it decomposes readily at slightly above the boiling point of water; For this reason it is more desirable to use an acid which is more resistant to pyrolysis. Similarly, when a polybasic acid is available in the form of an anhydride, such anhydride is apt to produce the ester with greater ease than the acid itself. For this reason, maleic anhydride is particularly adaptable, and also everything else considered, the cost is comparatively low on a per molar basis. even though somewhat higher on a per pound basis. Succinic acid or the anhydride has many attractive qualities of maleic anhydride, and this is also true of adipic acid. For purposes of brevity, the bulk of the examples, hereinafter illustrated, will refer to the use of maleic anhydride, although it is understood that any other suitable polybasic acid may be employed. Furthermore, reference is made to derivatives obtained by oxyethylation, although, as previously pointed out, other oxyalkylating agents may be employed.

As far as the range of oxyethylated glycerols Oxalic acid may employed as reactants is concerned, it is our preference to employ those in which approximately 15 to 24 oxyethylene groups have been introduced into a single glycerol molecule. This means that approximately five to eight oxyethylene radicals have been introduced for each original hydroxyl group.

The oxyalkylation of glycerol is a well known procedure (see Example 11 of German Patent No. 605,973, dated November 22, 1934, to I. G. Farbenindustrie A. G.). The procedure indicated in the following three examples is substantially identical with that outlined in said aforementioned German patent.

OXYETHYLATED GLYCEROL Example 1 184 pounds of glycerol is mixed with /2%, by Weight, of caustic soda solution having a specific gravity of 1.383. The caustic soda acts as a catalyst. The ethylene oxide is added in relatively small amounts, for instance, about 44 pounds at a time. The temperature employed is from 150-180 C. Generally, speaking, the gauge pressure "during the operation approximates 200 pounds at the maximum, and when reaction is complete, drops to zero, due to complete absorption of the ethylene oxide. When all the ethylene oxide has been absorbed and the reactants cooled, a second small portion, for instance, 44 more pounds of ethylene oxide, are added and the procedure repeated until the desired ratio of 15 pound moles of ethylene oxide to one pound mole of glycerol is obtained. This represents 660 pounds ofvethylene oxide for 92 pounds of glycerol.

OXYETHYLATED GLYCEROL Example 2 The ratio of ethylene oxide is increased to 18 pound moles for each pound mole of glycerol. Otherwise, the same procedure is followed as in Example 1, preceding.

OXYETHYLATED GLYCEROL Example 3 The same procedure is followed as in the two previous examples. except that the ratio of ethylene oxid to glycerol is increased to 21 to one,

OXYETHYLATED GLYoERoL MALEATE Example 1 One pound mole of oxyethylated glycerol (1 to 15 ratio) prepared in the manner previously described is treated with on pound mole of maleic anhydride and heated at approximately C,

for approximately thirty minutes to two hours, with constant stirring, so as to yield a monomaleate.

,OXYETHYLATED GLYCEROL MALEATE Example 2 The same procedure is followed as in the preceding example, except that two moles of maleic anhydride are employed so as to obtain the dimaleate instead of the monomaleate.

OXYETHYLA'EED GLYCEROL MALEATE Example 3 The same procedure is followed as in the two preceding examples, except that three moles of maleic anhydride are employed so as to obtain the trimaleate.

OxYErHYLA'rEn GLYCEROL MALEATE Example 4 The same procedure is employed as in the preceding examples, except that oxyethylated glycerol (ratio 1 to 18) is substituted in place of oxyethylated glycerol (ratio 1 to 15).

OXYETHYLATED GLYCEROL MALEATE Example i The same procedure is employed as in the preceding examples, except that oxyethylated glycare neutral or complete esters, as differentiated from fractional esters. The polyhydric alcohols employed'as reactants for the production of the neutral esters of the high molal hydroxy acids, are characterized by the fact that they may contain 2, 3 or 4' hydroxyl groups, the commonest examples being ethylene glycol, glycerol, and pentaerythritol. Other dihydric alcohols homologues of ethylene glycol, such as propylene F glycol, butyleneiglycol, etc., and include higher homologues. Still another variety is illustrated by the ether type of glycol, such asdiethylene glycol, dibutylene glycol, etc. It is not intended to include ether alcohols, particularly ether glycols, in which the ether linkageoccurs more than four times. Dihydric alcohols are also obtained by dehydroxylation of glycerol or the like, as, for example, by etherization with a monohydric alcohol; for instance, the methyl ether, ethyl ether, propyl ether, butyl ether, and similar alkoxy derivatives of glycerolQ Trihydric alcohols are illustrated most advantageously by glycerol. Similarly, etherization with monohydric alcohols,

yields trihydric alcohols from products such as diglycerol, pentaerythritol, mannitan, sorbitan, etc. The ethyl ether, butyl ether, or other alkoxy derivatives of diglycerol is an additional illustration of this. particular type. Alcohols containing four hydroxyls-may be illustrated by diglycerol, pentaerythritol, sorbitan, mannitan, etc.

I'he polyhydric alcohols just described are esterified with or converted by any suitable ineans intoivater-insoluble esters of high molal hydroxy acids having at least 11 carbon atoms and not in excess of 36 carbon atoms. The commonest ex- 7 ample of a high molal hydroxy acid is ricinoleic acid. Other hydroxy fatty acids include hydroxystearic acid, dihydroxystearic acid, diricinoleic acid,'aleuritic acid, andthe like. Similar acids are obtained in the oxidation of parafiin, petroleum hydrocarbons, or Wax, and are commonly referred to as hydroxylated wax acids.-

Hydroxylated wax acids occur as by-products in the oxidation of Waxes or similar materials, and

"are' usually separated so that the commonest commercial form of oxidized wax acids represent mixtures comparatively free from the hydroxylated compounds,

duced by other procedures, such as chlorination, 7 either by addition or substitution, as, for exam- Hydroxylated acids are proinclude of hydrochloric acid, instead of Water.

ple, chlorination of oleic acid or substitution, as, for example, chlorination of oleic acid or stearic acid. Subsequent reactions involve the removal of the chlorine with the introduction of a hydroxyl radical. Undecylenic acid, derived from castor oil, has been converted into a hydroxy undecenoic acid. Unsaturated hydroxy acids, such as ricinoleic acid, may be treated in various manners, so as to produce derivatives, for example, chlorinated or brominated ricinoleic acid. Such materials are entirely satisfactory for use as re-,

actants in the preparation of materialsof the kind herein contemplated. Naturally-occurring naphthenic acids can also be converted into hydroxylated products by following similar procedure. An unsaturated hydroxy acid, such as ricinoleic acid, can be converted into a hydroxylated arylstearic acid. Such procedure contemplates reactions such as those involving ricinoleic acid, benzene, and aluminum chloride in large excess, or involves the desulfonation of a sulfoaromatic fatty acid. In any event, by involving derivatives of undecylenic acid, or one or more of the various wax acids, naturally-occurring naphthenic acid, ricinoleio acid, diricinoleic acid, or derivatives thereof, as have been enumerated, one can obtain a variety of hydroxylated monocarboxy acids, having at least 11 carbon atoms and not in excess of 36 carbon atoms. Such compounds are the kind herein contemplated as reactants to furnish the alcoholiform hydroxyl.

Hydroxy acids of the kind herein contemplated may also be prepared by the hydrolysis of alphahalogen acids. For instance, alpha-bromocaproic acid, alpha-brornocaprylic acid, alphabromocapric acid, alphabromolauric acid, alphabromomyristic acid, alpha-bromopalmitic acid, and the like, can be hydrolyzed to give the corresponding alpha-hydroxy acid. Indeed, a reactive alpha-halogen acid may serve as a functional equivalent of an alpha-hydroxy acid by liberation type of reaction, however, involves numerous difficulties; and thus, it is better. to employ a hydroxy acid. I

In some instances derivatives of a hydroxylated unsaturated acid are most readily obtained by' th employment of an intermediate in which the hydroxyl group is protected. Thus, .ricinoleic acid may be. acetylated, and such acetyl ricinoleic acid converted into a derivative, for instance, a derivativein which an aryl group is introduced. Such derivative can then be saponified or hydrolyzed so as to regenerate the hydroxyl, radical.

As to the manufacture of various esters from acids of the kind above described, attention is directed to the following United States Patents: No. 1,160,595, dated Nov. 16, 1915, to 'Gruter et al.; No. 2,221,674, dated Nov. 12, 1940, to Ellisyand No. 2,177,407, dated Oct. 24, 1939, to Hensley. .lSggoalso Organic Syntheses, volume X, page 88,

COMPLETED MoNoMERIo DERIVATIVE Example 1 maleate, Example 1 is reacted with one pound mole of glycoldiricinoleate, preferably in the'ab-- senceof any high boiling hydrocarbon or inert solvent. However, if an inert vaporizing solvent is employed,,it is generally necessary to useione which has a higher boiling range than xylene and sometimes removal of such solvent might present a difficulty. In other instances, however,

Such I such high boiling inert vaporizing solvent, if employed, might be permitted .to remain in the reacted mass and appear as a constituent or ingredient of the final product. In any event, our preference is to conduct the reaction in the absence of any such solvent and permit the reaction to proceed with the elimination of water.

The temperature of reaction is about 180 to 200 C. and time of reaction about 20 hours.

COMPLETED MONOMERIC DERIVATIVE Example 2 The same procedure is followed as in Completed monomeric derivative, Example 1, preceding, except that the dimaleate described under the heading Oxyethylated glycerol maleate, Example 2 is used instead of the monomaleate.

COMPLETED MON'OMERIC, DERIVATIVE Example 3 The same procedure is followed as in the two preceding examples, except that the trimaleate is substituted for the monomaleate or dimaleate in the two preceding examples.

COMPLETED MONOMERIC DERIV TIVE Example 4 The same procedure is followed as in Examples 2 and 3, immediately preceding, except that for each pound mole of the dimaleate, or each pound mole of the trimaleate, instead of using one pound mole of ethylene glycol diricinoleate as a reactant, one employs two pound moles.

COMPLETED MONOMERIC DERIVATIVE Example 5 The same procedure is followed as in Example 3, preceding, except that for each pound mole of trimaleate, instead of adding one pound mole of ethylene glycol diricinoleate, one adds three pound moles of ethylene glycol diricinoleate for reaction. I

COMPLETED MONOMERIC DERIVATIVE Example 6 COMPL TED MONOMERIC DERIVATIVE Example 7 The same procedure is followed as in Example 6, immediately preceding, except that the oxyethylated glycerol employed represents one having an even higher degree of oxyethylation. For example, one indicated by the ratio of 1 to 21. (See Oxyethylated glycerol maleate, Example 5, preceding.)

COMPLETED MONOMERIC DERIVATIVE Example 8 The same procedure is followed as in Examples 1 to 7, preceding, except that di-ethylene glycol diricinoleate is substituted for ethylene glycol ricinoleate.

COMPLETED MoNoMERIc DERIVATIVE Example 9 The same procedure is followed as in Examples 1 to 7, preceding, except that dipropylene glycol diricinoleate is substituted for ethylene glycol diricinoleate.

COMPLETED MONOMERIC DERIVATIVE Example 10 The same procedure is followed as in Examples 1 to 7, preceding, except that glyceryl-alphamonomethyl ether diricinoleate is substituted for ethylene glycol diricinoleate. V

The method of producing such fractional esters is well known. The general procedure is to em: ploy a temperature above the boiling point of water and below the pyrolytic point of the reactants. The products are mixed and stirred constantly during the heating and esterification step. If desired, an inert gas, such as dried nitrogen or dried carbon dioxide, may be passed through the mixture. Sometimes it is desirable to add an esterification catalyst, such as sulfuric acid, benzene sulfonic acid, or the like. This is the same general procedure as employed in the manufacture of ethylene glycol dihydrogen diphthalate. (See U. S. Patent No. 2,075,107, dated March 30, 1937, to Frasier.)

Sometimes esterification is conducted most readily in the presence of an inert solvent, that carries away the Water of esterification which may be formed, although, as is readily appreciated, such water of esterification is absent when such type of reaction involves an acid anhydride, such as maleic anhydride, and a glycol. However if water is formed, for instance, when citric acid is employed, then a solvent such as xylene may be present and employed to carry off the water formed. The mixture of xylene vapors and water vapors can be condensed so that the water is separated. The xylene is then returned,

to the reaction vessel for further circulation. This is a'conventional and well known procedure and requires no further elaboration.

In the previous monomeric examples there is a definite tendency, in spite of precautions, at least in a number of instances, to obtain polymeric materials and certain cogeneric by-products. This is typical, of course, of organic reactions of this kind, and as is well known, organic reactions per se are characterized by the fact that yields are the exception, rather than the rule, and that significant yields are satisfactory, especially in those instances where the by-products or cogeners may satisfactorily serve with the same purpose as the principal or intentional product. This is true in the present instance. In many cases when the. compound is manufactured for purposes of demulsification, one is better off to obtain a polymer in the sense previously described, particularly a. polymer whose molecular Weight is a rather small multiple of the molecular weight of the monomer, for instance, a polymer whose molecular Weight is two, three, four, five, or six times the molecular weight of the monomer. Polymerization is hastened by the presence of an alkali, and thus, in instances where it is necessary to have a maximum yield of the monomer, it may be necessary to take such precautions that the alkali used in promoting oxyethylation of glycerol, be removed before subsequent reaction. This, of course, can be done in any simple manner by conversion to sodium chloride, sodium sulfate, or any suitable procedure.

In the preceding examples of the Completed monomeric derivative, Examples 1 to 10, inclusive, no reference is made to the elimination of such alkaline catalyst, in view of the eflfective ness of the low multiple polymers as demulsifiers. Previous reference has been made to the fact that the carboxylic hydrogen atom might be variously replaced by substituents, including organic radicals, for instance, the radicals obtained from alcohols, hydroxylated amines, nonhydroxylated amines, polyhydric alcohols, etc. Obviously, the reverse is also true, in that a free hydroxyl group may be esterified with a selected acid, varying from such materials as ricinoleic acid to oleic acid, including alcohol acids, such as hydroxyacetic acid, lactic acid, ricinoleic acid and alsopolybasic acids of the kind herein contemplated. I V V .With the above facts in mind, it becomes obvious that what has been previously said as to polymerization, with the suggestion that byproducts or cogeneric materials were formed, may be recapitulated with greater definiteness, and one can readily appreciate that the formation of heat-rearranged derivatives or compounds must take place to a greater or lesser degree; 7 Thus, the products herein contemplated may be characterized by being monomers of the type previously described, or esterification polymers, or the heat-rearranged derivatives of the same, and thus including the heat-rearranged derivatives of both the polymers and esterification monomers, separately and jointly. Although the class of materials specifically contemplated in this instance is a comparatively small and narrow class of a broad genus, yet

it is obviously impossible to present any adequate' formula which would contemplate the present series in their complete ramification, ex-

cept in a manner employed in the hereto appended claims.

Although the products herein contemplated vary so broadly in their characteristics, i. e.,

monomers through sub-resinous polymers, solub-le products, Water-emulsifiable oils or comethylation of the glycerol used as the raw material'. When our new product is used as a demulsifier, in the resolution of oil field emulsions, thedemulsi'fier may be added to the emulsion at the ratio of 1 part in 10,000, 1 part in 20,000, 1 part in 30,000, or for that matter, 1 part in 40,000. In such ratios it well may be that one can not differentiate between the solubility of a, compound completely soluble in water in any ratio, and a semi-resinous product apparently insoluble in water in ratios by which ordinary insoluble materials are characterized. However, at such ratios the importance must reside in interracial position and the ability to usurp, preempt, or replace the interfacial position previously occupied perhaps by theemulsifying colloid. In any event, reviewed in this light, the obvious common property running through the entire series, notwithstanding variation in molecular size and physical make-up, is

absolutely apparent. Such statement is an obvious oversimplifi'cation of the rationale underlying demulsification, and does not even consider the resistance of an lnterfacial film to crumbling, displacement, being forced into solution, altered wetability, and the like. As to amidification polymers, for instance, where Z is a polyaminoamide radical, see what is said subsequently.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED' COGENERS Example 1 One pound mole of oxyethylated glycerol dimaleate is reacted with on'e'pound mole of ethylene glycol diricinoleate fora period of two to 60 hours, at a temperature of approximately 220- 240 C., with constant stirring, so as to eliminate sufiicient water, in order to insure that the re sultant product has a molecular weight approximately twice that of the initial monomer.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANCED COGENERS Example 2' The same procedure is followed as in the preceding example, except that polymerization is continued, using either a somewhat longer reaction time, or it may be, a somewhat higher temperature, or both, so as to obtain a material having a molecular weight of approximately three to four times that of the initial product.

CCMPL TED POLYMERIC DERIVATIVES INCLUllING HEAT-REARRANGED COGENERS Example 3 The same procedure is followed as in Examples 1 and 2, preceding, except that one employs as reactants a more highly oxyethylated glycerol and diethylene glycol diricinoleate, instead of ethylene glycol ricinoleate.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED CocENERs Example 4 The same procedure is followed as in Examples 1 to 3, preceding, except that one polymerizes a mixture instead of a single monomer, for instance, a mixture ofv materials of the kind described in Completed monomeric derivative, Example 3, and, in Completed monomeric derivative, Example 4, are mixed in molecular proportion and subjected to polymerization in the manner indicated in the previous examples.

7 It is understood, of course, that the polymerized product need not be obtainedas a result of a two-step procedure. In other words, one need not convert the reactants into the monomer and then subsequently convert the monomer into the polymer. verted through the monomer to the polymer in one step. Indeed, the formation of the (mono mer and polymerizationmay take place simultaneously. This is especially true if polymerization is conducted in the absence of an inert solvent, as previously described, and if one uses a comparatively higher temperaturaior instance, approximately 220 C. for polymerization. Thus, one pound mole of oxyethylated glycerol mal'eate of the kind described, ratio 1 to 15, up to l to 21, is mixed with two moles of ethylene glycol diricinoleate and reacted for 30 hours at approximately 220 C. until the mass is homogeneous. It is stirred constantly during reaction. Polyfunctionality may reside in dehydration (etherization) of two hydroxyl groups attached to dissimilar molecules. L

The reactants may be con- 7 The fact that the polymerized and heat-rearranged products can be made in a single step, illustrates a phenomenon which sometimes occurs either in such instances where alcoholic bodies of the kind herein illustrated are contemplated as reactants, or where somewhat kindred alcoholic bodies are employed. The reactants may be mixed mechanically to give a homogeneous mixture, or if the reactants do not mix to give a homogeneous mixture,-then early in the reaction stage there is formed, to a greater or lesser degree, sufiicient monomeric materials so that a homogeneous system is present. Subsequently, as reaction continues, the system may become heterogeneous and exist in two distinct phases, one being possibly an oily body of moderate viscosity, and the other being a beaver material, which is sticky or sub-resinous in nature. In many instances, it will be found that the thinner liquid material is a monomer and the more Viscous or resinous material is a polymer, as previously described. Such product can be used for demulsification by adding a solvent which will mutually dissolve the two materials, or else, by separating the two heterogeneous phases and employing each as if it were a separate product of reaction.

Materials of the kind herein contemplated may find uses as wetting, detergent, and leveling agents in the laundry, textile, and dyeing industry; as wetting agents and detergents in the acid washing of fruit, in the acid Washing of building stone and brick; as a Wetting agent and spreader in the application of asphalt in road building and the like, as a constituent of soldering flux preparations; as a flotation reagent in the flotation separation of various minerals; for flocculation and coagulation of various aqueous suspensions containing negatively charged particles such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifiers for cosmetics, spray oils, water-repellent textile finish, etc. These uses are by no means exhaustive.

However, the most important phase of the present invention, as far as industrial application goes, is concerned with the use of the materials previously described as demulsifiers for water-in-oil emulsions, and more specifically, emulsions of water or brine in crude petroleum. We have found that the particular chemical compounds or reagents herein described may also be used for other purposes, for instance, as a break inducer in doctor treatment of the kind.

intended to sweeten gasoline. (See U. S. Patent No. 2,157,223, dated May 9, 1939, to Sutton.)

Chemical compounds of the kind herein described are also of value as surface tension depressants in the acidization of calcareous oilbearing strata by means of strong mineral acid, such as hydrochloric acid. Similarly, some members are effective as surface tension depressants or wetting agents in the flooding of exhausted oil-bearing strata.

As to using compounds of the kind herein described as flooding agents for recovering oil from subterranean strata, reference is made to the procedure described in detail in U. S. Patent No. 2,226,119, dated December 24, 1940, to De Groote and Keiser. As to using compounds of the kind herein described as demulsifiers, or in particular as surface tension depressants in combination with mineral acid or acidization of oilbearing strata, reference is made to U. S. Patent No. 2,233,363, dated February 25, 1941, to De Groote and Keiser.

Cognizance must be taken of the fact that the surface of the reacting vessel may increase or decrease reaction rate and degree of polymerization, for instance, an iron reaction vessel speeds up reaction and polymerization, compared with a glass-lined vessel.

As has been previously indicated, the subgenus employed as an alcohol in the present instance is one of a series of alcoholic compounds which are contemplated in our co-pending applications Serial Nos. 497,118, 497,119, 497,120, 497,121, 497,122, 497,123, 497,124, 497,125, 497,127, 497,128, 497,129, 497,130, 497,131, 497,132, 497,133, 497,134, and 497,135, all filed August 2, 1943.

Having thus described our invention, what We claim as new and desire to secure by Letters Patent is:

1. An ester, being a member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives thereof and of the following formula:

in which R is the carboxyl-free radical of a polycarboxy acid having not over 8 carbon atoms; R1 is a water-insoluble polyhydric alcohol acid radical, the acyl radical of which being a high molal hydroxy acid acyl radical having at least 8 carbon atoms and not more than 32 carbon atoms; the alcohol radical ofsaid ester radical having a valency of at least two and not more than 4, and said ester radical containing hydroxyl groups as part of the acyl radical only; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; 11. represents the numerals 2 to 4; n represents the numerals 3 to 10; n" represents the numerals 1 to 2; a: represents the numerals 0 to 2; 11 represents the nu merals 0 to 2; 2 represents the numerals 1 to 3; ac represents the numerals 0 to 1; and y represents the numerals 1 to 2.

2. An ester, being a member of the class consist-. ing of monomers, sub-resinous esterification polymers, and cogenerio sub-resinous heat-rearranged derivatives thereof and of the following formula:

in which R is a carboxyl-free radical of a dicarboxy acid having not over 6 carbon atoms; R1 1 is a water-insoluble polyhydric alcohol acid radical, th acyl radical of which being a high molal hydroxy acid acyl radical having at least 8 carbon atoms and not more than 32 carbon atoms; the alcohol radical of said ester radical having a valency of at least two and, not more than 4, and said ester radical containing hydroxyl groups as part of the acyl radical only; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; 11 represents the numerals 2 to 4; n represents the numerals 3 to 10; x represents the numerals 0 to 2; 31 represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

3. An ester, being a member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives thereof and of the following formula:

[(cnnon'oooRoooz]z O3H5O3-"[(C2H4O 1.'H]y

[(CzHaOLuO O C RC 0 R1];

in which R is a carboXyl-free radical of a dicarboxy acid having not over 6'carbon atoms; R1

is a water-insoluble polyhydric alcohol acid radical, the acyl radical of which being a high molal hydroxy acid acyl radical having at least 8 carbon atoms and not more than 32 carbon atoms; the alcohol radical of said ester radical having a 1 valency of at least 2 and not more than 4; and

said ester radical containing hydroxyl groups as partof the acyl radical only; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; 11' represents the numerals 3 to :0 represents the numerals 0 to 2; y represents the numerals 0 to 2; and 2 represents the numerals l to 3.

' 4. An ester, being a polar member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heatrearranged derivatives thereof and of the following formula:

in which R is a carboXyl-free radical of a dicarboxy acid having not over 6 carbon atoms; R1 is a water-insoluble polyhydric alcohol acid radical, the'acyl radical of which being a high molal hydroxy acid acyl radical having at least 8 carbon atoms and not more than 32 carbon atoms; the alcohol radical of said ester radical having a valency of at least 2 and not more than 4, and said ester radical containing hydroxyl groups as part of the acyl radical only; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; 11 represents the numerals 2 to 4; n represents the numerals 3 to 10; :t'; represents the numerals 0 to 2;, 3 represents the numerals 0 to 2; and .2 represents the numerals 1 to 3. I 5. An ester, being a polar acidic member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives thereof, and of the following formula:

[(C2H4O)n'OOORCOOZ] CaHt a-[( 2H4O)n' ]i olHlo),, oooRoo0R1].

in which R is a carboxyl-free radical of a dicarboxy acid having not over 6 carbon atoms; R1 is a water-insoluble polyhydric alcohol acid radical, the acyl radical of which being a high molal hydroxy acid acyl radical having at least 8 carbon atoms and not more than 32 carbon atoms; the alcohol radical of said ester radical having a valency of at least two and not more than 4, and said esterlradical containing hydroxyl groups as part of the acyl radical only; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10 :c represents the numerals 0 to 2; ,1; represents the numerals 0.to 2; and 2 represents the numerals 1 to 3.

6. An ester, being a polar acidic member of the class" consisting of monomers, subresinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives thereof, and of the following formula:

in which R is a carboxyl-free radical of a dicarboxy acid having not over 6 carbon atoms; R1 is a water-insoluble diol ester radical in which the acyl radicals contain 18 carbon atoms and at least one hydroxyl radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself'; n represents the numerals 3 to 10; :1: represents the numerals 0 to 2; y represents the numerals 0 to 2; andz represents the numerals 1 to 3.

7. An ester, being a polar acidic member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives thereof, and of the following formula:

in which R is a carboxyl-free radical of a dicarboxy acid having not over 6 carbon atoms; R1 is a diol diricinoleate radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; :1: represents the numerals 0 to 2; y represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

8. An ester, being a polar acidic member of the class consisting of monomers, sub-resinous in which R is a carboxyl-free radical of a dicarboxy acid having not over 6 carbon atoms; R1 is an ethylene glycol diricinoleate radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; n: represents the numerals 0 to 2; 11 represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

9. A. method for manufacturing esters as defined in claim 1, consisting of reacting an oxyalkylated glycerol with a polycarboxy acid having not over 8 carbon atoms, and subsequently reacting said intermediate product with a water-insoluble' polyhydric alcohol ester, the acyl radical of which being a high molal hydroxy acil acyl radical having atleast 8 carbon atoms and not more than 32 carbon atoms, the alcohol radical of said ester having a valency of at least 2 and not more than 4, and said ester radical containing hydroxyl groups as part of the acyl radical 

